Catalytic alkylation of aromatic hydrocarbons by long chain olefins



P. .HILL

Mucha, 194s.

CATALYTIC ALKYLATION OF AROHATIC HYDROCARBONS BY-LONG CHAIN OLEFINS Filed'uarcn 27, v1945 .wxs kann hun@ bskoudwtb Patented Mar. 9, 1948 CATALYTIC ALKYLATIN F AROMATIC lBOCABBONS BY LONG CHAIN OLE- Philip Hill, Hammond, Ind., assignor to Standard Oil Company. o! Indiana Chicago, lll., a corporation Application March 27, 1945, Serial No. 585,123

matic hydrocarbons. More particularly it relates to 'the allwlation of aromatic hydrocarbons with oleiinic hydrocarbons of high molecular weight to yield alkylates who suli'onates are preferentially soluble in hydrocarbon oils.

As used in this specification and the appended claims, the term alkylation" is intended to designate the reaction between an aromatic hydrocarbon and an olefin wherein-.the net eiect of the reaction is the replacement of a hydrogen atom on a nuclear' carbon atom of the aromatic hydrocarbon by an alkyl group having the same number of carbon atoms as the oleiln.

The present invention finds its preferred application in the alkylation of aromatic hydrocarbons, particularly monocyclic aromatic hydrocarbons, with aluminum chloride and a minor proportion of hydrogen chloride. In this type of alkylation reaction, olenic hydrocarbons having less than about 15 carbon atoms in the bons, by which I mean oleiinic hydrocarbons having at least l carbon atoms, especially 20 or more carbon atoms, e. g., 25, 30, 40, or 50 carbon atoms in the molecule, do not alkylate well, that is to say, they require relatively gross amounts oi?` aluminum chloride catalyst, long reaction periods and aiIord relatively poor yields. Attempts toy overcome the sluggish behavior of higher oleilnic hydrocarbons in these alkylation reactions by the employment of more severe operating conditions, such as high alkylation temperatures, high proportions of catalysts, or long reaction periods are unsuccessful. Failure to lmprove the alkylation reaction. by the selection of relatively severe operating conditions may be attributed primarily to the fact that these conditions induce decomposition of the higher oleiinic hydrocarbon to produce products having both more and less carbon atoms in the molecule than the oleflnic feed stock, and these degradation products may then alkylate the aromatic hydrocarbon to produce nondescript alkylates of wide boiling range containing a greatly reduced proportion or the desired alkylation product. Also, severe operating conditions tend to destroy the alkylate produced from the feed stocks.

This invention is concerned primarily with the production oi' alkyl aromatic hydrocarbons, particularly monocyclic aromatic hydrocarbons, having one or more side chains containing at least l5l carbon atoms. Alkyl aromatic hydrocarbons of this description are eminently suitable 12 Claims. (Cl. 2130-671) 2 for sulfonation to yield sulfonic acids whose salts, i. e., soaps, are either preferentially soluble in hydrocarbon oils or highly soluble in hydrocarbon oils and quite insoluble in water at ordinary temperatures. Soaps of this type may be regarded as synthetic" mahogany soaps. These soaps are capable of specialized applications which necessitate the placement of rigid specifications on the soaps, one of the speciiications being the absence' of preferentially water soluble soaps. Preferentially waterL soluble soaps result from the sulfonation and neutralization of alkyl aromatic hydrocarbons having less than 15 carbon atoms in the alkyl group. Therefore it is essential. in the preparation of a preferentially oil soluble alkyl aromatic hydrocarbon sulfonate, to employ alkylaromatic hydrocarbons containing no substantial proportion of constituents having less than 15 carbon atoms in the alkyl group.

In a preferred embodiment, this invention relates to the alkylation of an aromatic hydrocarbon with a selected olenic hydrocarbon or a mixture of olenic hydrocarbons of relatively narrow boiling range and restricted variation in the number of carbon atoms in the molecule, to produce alkylates of relatively narrow boiling range and restricted variation in the number of carbon atoms in the molecule. More particularly, the invention relates to the alkylation of benzene or similar hydrocarbons with olellns having at least 15 carbon atoms in the molecule and of restricted molecularweight range, i. e., olen fractions having about 15 to 21 carbon atoms in the molecule or-about 20 to 30 carbon atoms in the molecule, without substantial concomitant production of alkyl benzenes having less than about 15 alkyl carbon atoms in the molecule. In my invention, no substantial proportion, e. g., not more than about 5%, of olefinic hydrocarbons having a molecular weight between about and 210 is included in the feed stock.

It is an object of my invention to provide an improved process for the alkylation of aromatic hydrocarbons with olenic hydrocarbons having at least 15 carbon atoms in the molecule in the presence of a catalyst of the type of aluminum chloride and a minor proportion of hydrogen chloride. Another object' of my invention is to provide a process for the alkylation of monocyclic aromatichydrocarbons with olenic hydrocarbons having at least 15 carbon atoms in the molecule to produce alkyl aromatic hydrocarbons whose alkyl groups contain at least 15 carbon atoms without substantial production of alkyl aromatic hydrocarbons whose alkyl groups contain less than 15 carbon atoms. An additional object of my invention is to provide a process for the alkylation of aromatic hydrocarbons such as benzene with olenic hydrocarbons containing at least 15 carbon atoms in the molecule in the presence oi' a catalyst of the type oi' aluminum chloride promoted by a minor proportion of hydrogen chloride, which process is characterized by improved yields of desired alkylate, lower catalyst requirements and consumption, lower reaction temperatures, and shorter reaction periods for a given yield.

Briefly, this invention relates to the employment of a minor proportion, less than about of a. lower olenic hydrocarbon having a molecular weight below about 130 to facilitate the alkylation oi' an aromatic hydrocarbon, particularly a monocyclic aromatic hydrocarbon, by an olelinic hydrocarbon or a mixture of olefin-ie hydrocarbons having at least carbon atoms in the molecule in the presence of a. catalyst such as aluminum chloride promoted by a minor proportion of hydrogen chloride. Suitable lower oleiinic hydrocarbons which may serve as promoters in the aikylation of aromatic hydrocarbons such as benzene and the like with higher oleilnic hydrocarbons include various octen'es, heptenes, hexenes,'pentenes, butenes, etc. I may also employ lower molecular weight cyclo-oleilns such as cyclohexene. methylcyclohexene, cyclo-4 pentene, and methylcyclopentene. Although I 4- Suitable aromatic hydrocarbons may be de` rived from fractionation or other puriilcation procedures applied to coal, coal tars, or hydrocarbon oil mixtures, produced by conversion and/or solvent extraction. e. g., hydroforming of naphthas, hydrogenation of oils, dehydrogenation oi.' naphthenes such as cyclohexane. methylcyclohexane and the like, coking of hydrocarbon oils, thermal or catalytic cracking of hydrocarbon oils, coal hydrogenaizion, etc.

A wide varietyol' higher oleinic hydrocarbons having at least l5 carbon atoms inl the molecule may .be used as alkylating agents for the purposes of this invention. I may use either pure or mixed olenic hydrocarbons. Normally I prefer to use a mixture of olefinic hydrocarbons having a relatively restricted molecular weight range. Suitable higher olefinic hydrocarbon feed stocks may be prepared by polymerizing lower molecular weight oleiins; epecially in the presence of a catalyst. e. g., an aluminum chloride-hydrocarbon complex and hydrogen chloride as described in U. S. patent applications S. N. 510,112 led by B. L. Everlng et al., on

prefer to employ aliphatic olenic hydrocarbons,

I may employ other oleilnic materials-such as styrene, vinylfurane, vinylacetylene, vinylpyridines, methyl vinyl ketone, vinyl acetate, and the like. It will be understood that the lower molecular weight olenic hydrocarbon need not be employed in the pure form. 'Ihus the ole-.- iinic hydrocarbon Vmay contain non-reactive, non-deleterious materials such as normal. parafiins and the like. Also, it is possible to employ a mixture o! two or more lower oleinic materials.

I have found that the addition of a minor proportion oi' a. lower oleiinic hydrocarbon having a molecular weight below about 130 to an alkylatlon zone wherein benzene is being alkylated with a higher olenic hydrocarbon having at least 15 carbon atoms in the molecule in the presence of a catalyst of the type orV aluminum chloride promoted by a minor proportion of hydrogen chloride exerts a promoting eiIect upon the alkylation reaction, rendering possible the use of much shorter reaction periods, proportions of catalyst, and temperatures than would be possible in the absence of said lower oleilnic hydrocarbon. Furthermore, the .presence of the lower olefinic hydrocarllon results in increased yields of desired alkylate and inn hibits or prevents the cracking or degradation of the higher molecular weight olenic feed stock and the production of undesired alkylates of lower and higher molecular weight than that which would be produced by the chemical union of the aromatic hydrocarbon and higher molecular weight olen feed stocks.

Particularly suitable aromatic feed stocks are monocyclic aromatica, especially benzene and the like. The process oi' my invention may also be applied to alkyl substituted benzenes such as toluene, xylene, cumene, n-propyl benzene, trimethylbenzenes, triethylbenzenes, and the like. My invention may also be applicable to the alkylation of monocyclic aromatics containing one or more non-hydrocarbon nuclear `substituents, e. g.. amino, N-substituted amino, amido, nitro, halogen, or Q-R groups wherein R" is a hydrocarbon radical. carbonyl, carboxyl groups, and the like.

November 13,1943, now U. S. Patent 2,407,873, issued September l'l, 1946, and S. N. 466,286, led :by D. E. Burney et al., on November 20, 1942, now U.- S. Patent 2,397,945, issued April 9, 1946. Oleiinic feed stocks may also be Prepared by dehydratlng higher molecular weight alcohols hav- Ling the same number of carbon atoms as that desired in the oleiinic hydrocarbon. e. s., myristyl, palmityl, stearyl alcohols and the like, using a variety of catalysts, e. g.. alumina, phosphoric acid and acid-acting metal salts, such as NiClz, MgCl2, etc. A desirable source of high molecular weight olefins is paraiiin wax which may be catalytically dehydrgenated over sixth group metal oxides or cracked in the vapor phase at high temperatures to yield the desired olens. Numerous other methods of preparing olens are known and need not be detailed here. Higher olenic hydrocarbons are applicable in my process regardless of their source or method of manufacture.

I prefer particularly to employ higher oleiinic hydrocarbons of straight chain or slightly branched chain structure, e. g., oleiins produced by polymerization of a normal olefin hydrocarbon such as ethylene, propylen'e, butene-l, butene-2, and the like. For purposes of illustration, Table I is included to depict representative fractions of a polymer prepared by polymerizing propylene with an aluminum chloride catalyst.

Table I Properaer of proprlen polymer iam jract Mohr Wt. Bolling (clim A Fraction Range Np From in (t mm.) Bmnane h 1| Il d* Number) l. 4457 213 15. 2 l. 4484 240 17. 1 l. 4511 31 1.8.,6 l. 45m m 19. 1 l. 4541 291 m. s l. 4562 m 2l. 0 L 4578 m n s l. 45m m m. 4 l. 4610 348 24. s l. 4623 372 L 4634 m a. e

I may use any one or a compodte of two or more of the fractions shown in Table I for the alkylation or an aromatic hydrocarbon such as benzene to produce alkylates suitable for the v manufacture of preferentially oil soluble 'alkyl aromatic hydrocarbon sulfonates.

In my alkylation process I may feed aromatic hydrocarbons and the higher olenic hydrocar- 5 bon into the alkylation reactor in mol ratios of [at least one but preferably two or more. e. g., ve

or even ten. When the aromatic hydrocarbon is benzene, I prefer to feed it into the alkylation reactor in a mol ratio between about 2 and about l0 5 with respect to the higher oleilnic hydrocarbon. My preferred catalyst is aluminum chloride and a minor proportion of a hydrogen halide, particularly hydrogen chloride. Ordinarily I use about 0.5 to about 5% by weight of aluminum chloride/15 based on olen hydrocarbon, preferably about/ 2 to about 3 weight percent. The hydrogen halide may be used in proportions of about 5 to about 30 weight percent based on AlCls. My invention may also be effected with other Friedel-Crafts catalysts of the type of aluminum chloride, e. g., BFa. HF, and halides, e. g., chlorides, of Fe, Sn, Zn, Be, cb, Ge, Ti. zr, and Hf.

Alkylation of aromatics with the higher oleiinic hydrocarbons can usually be effected at temperatures in the range of about 0 to about 150 F. The alkylation of benzene can usually be effected at temperatures in the range of about 0 to about 100 F., preferably about 30 to about 90 F. The

hydrocarbon reactants are maintained in the liquid phase throughout the reaction. Alkylation may often be effected at atmospheric pressure but higher pressures, e. g., about 50 to 500 p. s. i., may sometimes be necessary or convenient.

The accompanying figure illustrates one embodiment of the process of my invention. As shown, the aromatic hydrocarbon, e. g., benzene, and higher oleiinic feed stocks are charged via lines I and 2 into an alkylation reactor 4. The

lower olefinic hydrocarbon is charged into reactor an aluminum chloride-hydrocarbon complex produced in the alkylation reaction or in some other reaction and passed into line 9 via line 32. An aluminum chloride-hydrocarbon complex may be produced by agitating granular aluminum chloride with a portion of the lower oletlnic hydrocarbon and a minor proportion of HC1 at temperatures in the range of about 30 to about 90 F. and the resulting complex may -be passed into reactor 4 via. lines 41 and 9. The use of a pre-formed aluminum chloride complex with the lower oleflnic hydrocarbon tends to reduce the amounts of lower olenic hydrocarbon which it is necessary to add to the reaction mixture in the allwlation reactor. Hydrogen chloride is passed into the reactor by lines I0 and II. In the reactor, the catalysts and 65 feed stocks are thoroughly agitated and thereafter are passed through an opening in bale 'l into the upper quiescent zone 8. Suitable operating conditions in the alkylation reactor are a temperature in the range of about 30 to about 70 90 F., a pressure in the range of about 0 to about 50 p. s. i. g. and a reaction time between about 5 and about 30 minutes. preferably between' about 10 and about 15 minutes.

Products are withdrawn from the reactor by 6 y valved lline I2 and may be passed through a heat exchangene. g., cooler I3, to a settler I4. Part or all of the products may by-pass the cooler by employment of valved line I5. The settler is preferably maintained at about the. same temperature and pressure as the reactor. Two liquid phases are formed in settler I4; the upper phase contains principally alkylation products and unreacted feed stock, and absorbed hydrogen chloride. 'I'he upper\ l,iquid phase is removed from settler I4 by valved line I6 into HC1 stripper 43.

The lower liquid phase ln settler I4 comprises 'principally a complex of aluminum chloride with hydrocarbons, diluted more or less by absorbed hydrocarbons and possibly containing some dissolved aluminum chloride. This lower liquid phase is removed from the settler through line 23and is passed into the lower portion of a complex stripper 24. Stripper/24 maybe provided with gas-liquid contact devices such as foraminous plates, bubble cap trays, screens, ceramic bodies, and the like. In the stripper, heat is applied to the contents by means of a heating coil 25; alternatively or in addition, the stripper may be heated by the injection `of hot inert gas, e. g., methane, ethane, propane, flue gases, or the like. Occluded or absorbed hydrocarbons are vaporized and fractionated in stripper 24 and pass overhead through valved line 28 to line 2| to join the stream of products passing to fractionator 22.

The HC1 stripper 43 may suitably be operated at a bottoms temperature in the range of about 200 to about 250 F. and a pressure in the range of about 0 to about 50 p. s. i. g. The gases and vapors pass overhead from stripper 43 `into line 44, pass through a cooler I1 and are pumped by pump 45 into the lower portion of an absorber I8. The use of a hydrogen chloride absorber is highly desirable to insure low hydrogen chloride consumption. Absorption and recycle of this stripped hydrogen chloride to the reactor maintainsvoptimum allwlation conditions therein. The absorber may be provided with conventional gas-liquid contact means. In the absorber, the gases and vapors introduced are countercurrently con-v tacted with a, liquid medium which serves as ja solvent for hydrogen chloride. The liquid abfsorption medium may be an aluminum chloride-Iy hydrocarbon complex produced in the alkylation process of this invention or in other hydrocarbon conversion operations. Other suitable absorption media are hydrocarbon oils, e. g., mineral seal oil' or other absorber oils, a portion of the aromaticl feed stock, or by-product, high molecular weight alkylates which may be produced in the alkylation process of this invention. It is preferred to use an absorption medium such as a portion of the aromatic feed stock which takes part inthe 30 to about 300 p. s. i. g. Unabsorbed gases leave absorber I8 by line 20' and may be subjected to a second absorption operation or be discarded from.

the system.

Liquid products containing some unreacted maf-fi terials pass from `HCl stripper 43 by line 46 into line 2l and thence to fractionator '22. In fractionator. 22, alkylation products andunreacted feed stocksare separated. Idght hydroczaubons v may be discarded from the fractionator by line esonero `l". Um'eoetedaromatichydrocarbons and other materialsofsimilarboilingrangemayberemoved from the fractionatonby means otline 28, and mayberecycled wholly orinjpart to reactor t .(byalinenotshown). Thedelired alkylation productisremoved liractionatorhyline 2l: `.it ahiahly-desirabie i'eed vstock for sulfonation to form preferentially oil soluble sulionates auch as synthetic mahogany soaps. A relattvdyramallpmportion-of heavy products may be termed and is removed from the fractionator byvnvea'nneu. mnesvy indemnitybeau-` thereof cardedfor allora fraction may be cycled `toebsorber It toserveasanabemption medium.

Stripped aluminum `chloride co lex leaves stripper Ilhy line Il and all or a i' maybecycledtothereactorviavalved lines 32 and 0. line. may be provided with mixing de vis. e. s.. DBM venturis. ctc.. to assure thorouch admmme or `recycled aluminum chloride complex and added aluminum chloride. A fraction of the .aluminum chloride complex may be cycled to il by vai'ved lines 8l and Il toserveasan-abeorption'medimn when a substantial `reduction 'in the reactivity of the aluminum chloride complex occurs, it may be cycled i'roln the complex stripper to a regeneration system indicated `schematically by 3l via valved lines 3| and Il. suitable aluminum chloride-hydrocarbon complex regeneration system may involve catalytic hydrogenation of the complex. as describedin U. `S. Patent 2,348,408, of James N1. Page, Jr. The regenerated complex may-be reeyeledtoreactorl bymeansoflines 3l, 31.82, and 0, Y Y

`lillorpartofthecatalytioaliyinactive complex mayalso be passed from stripper Il to a hydrogen 'chloridegenerator ll by means ofvalved lines 3l and Il. In the hydrogen chloride generator 30,' the aluminum lchloride ,bound in the spent oomplex is hydrolysed by reaction with water, steam,

onthereof Y `aqueous sulruricacidor other hydrolyzina media introduced by line Il, remlting in theseneration of hydrogen chloride which is cycled to the reactorlbylinesll, il. and I I. Non-gaseousproducts formed in the hydrosen chloride generator include alumina and cokey and liquid hydrocarbons which are withdrawn by line 42 for subsequent treatment which may include iiltration or settling. decanting Aiiiillid hydrocarbons and fractionation oi the liquid hydrocarbons.

The following tabulation sets forth experimental data which are illustrative, but not limitative, of the improved and `unexpected results ob' tainable by my improved alkylation process. The higher oleiinie hy named as a charging stock in Table 1I were obtained by polymerizing a petroleum renery propylene fraction with an `aluminum chloride catalyst and had an average molecular weight of about 300 indicating that the average carbon chain length in the polymer was 21.5 carbon atoms: the carbon chainlength varied from about 19 to about 23 carbon atoms. A..S.T.M. distillationanalysisofthehisher oleiinic hydrocarbons was ss follows:

Pn'omtDiltilhd The maximum distillation temperature ot the higherolenlcwas'll?. The

lowerolevnnichydrocarbomsetforthalacharsme stock .in Table II were... Baht traction obtained by polymerization o! a rennery propylene fraction with aluminum chlorid'efboiiing in the renee of about 200 to about 350 Ii'. and containingcarbon'chainsintherangeofaboutCeto Cu. predominating in Ca to 0|. The technical amylenes set forth as a charging stock in Table 1I were amixtureofpentenes Kodak technical amylenes); f

In the experiments reported in Table 1I, benzene was saturated with HCl las at room temperature (ca. FJ, and powdered AlCh was added with stirring. The polymer was then added to the reaction mixture at such a rate that the reaction temperature could be maintained at -90" F. by means of an ice-water bath. stirring was then continued for the ,intervals set forth in the table. In experiment 4, the low reaction tem.. perature was maintained with a dry ice-alcohol bath. Addition took a much longer time because of the necessity of maintaining a low temperature.

The courses of the alkylation reactions set forth in Table II were followed by titration of small samples with bromine, samples being taken from the reactor from time to time. The theoretical Vbromine absorption of the alkylation product is, of course. zero, using bromination conditions which are selective for an oleiln double bond.

Table Il Alkylation of benzene Experiment -i2`s Chmn Volume oi higher oleilnlo hydrocarbons, ml Weight ot higher oleilnic hydrocarns, Vgloumegoli lower oleiiuio hydrocarns, in

Volume o! technical amylenes ml Volume or benzene (saturated with HC1 at room temperature), ml..-.. m0 Weight A101.. g 6 Time for polymer addition, min 5 Reaction tempera F 85-00 Unsstuxation in alky tion mixture (mi. 0.6 Bri/ml. soin.) Initial 4. 17 .After minutes stirring 1. 38

Aitor 20 minutes stirring Alter 25 minutes stlrrinr l. 02 Alter 30 minutos ltirring Alter 40 minutes stirrinr i 0. 67 .alter o0 minutes stirrina 0. 66

ias s s s l HC1 pas bubbied through reaction mixture for about 2 minutes to assure sanitation.

It will be observed from the data of Table II that in experiment l, alkylation was'only 84% complete after one hour, while in experiment 2, identical except forthe inclusion of 4% of lower oleilnic hydrocarbons, 96% alkylatlon was achieved in l0 minutes and 100% alkylation in less .than 20 minutes. Experiment 3 indicates that amylenes are satisfactory promoters for the alkylation reaction, provided that care is taken to keep the alkylation reaction mixture saturated with HC1 gas. Experiment 4 indicates that the alkylation may be eected satisfactorily at a low temperature and with a short reaction period when o.' lower oleiinic hydrocarbon is employed to promote the reaction. The ability to alkylatesatisfactorily at low' temperatures is important, since, as previously mentioned, cracking of the higher molecular weight oleiln and alkylates is avoided with consequent increase in the yield of desired alkylation product. Reduction in the extent of cracking in the alkylation reaction also reduces the required fractionation capacity of the alkylaf tion plant.

annate 9 It will be apparent that I have provided a novel and improved process for the alkylation of aromatic hydrocarbons, particularly to produce higher alkyl aromatic hydrocarbons suitable for the sulfonation to form oil soluble or Preferentially oilsoluble sulfonates.

1. In the alkylation of an aromatic hydrocarbon with a higher mono-oleiln hydrocarbonfhaving at least 20 carbon atoms in the molecule in the presence of a Friedel-Crafts catalyst, the improvement which comprises effecting said allwlation in the presence of a minor proportion, based on said higher mono-oleiln hydrocarbon. of an added lower olenic hydrocarbon having a molecular weight not in excess or about 130. A

2. 'I'he process of claim 1 wherein the higher mono-olen hydrocarbon is prepared by polymerization of a normal mono-olen hydrocarbon.

3. The process of claim 1 wherein the aromatic hydrocarbon is benzene.

4. 'I'he process of claim 1 wherein the aromatic hydrocarbon is a monocyclic hydrocarbon and the Friedel-Crafts catalyst is aluminum chloride, promoted by a minor proportion of hydrogen chloride.

5. In the alkylation of benzene with a polymer of a normal mono-olen hydrocarbon, said polymer having at least 20 carbon atoms in the molecule in the presence of aluminum chloride and a minor proportion of hydrogen chloride, the improvement which comprises effecting said alkylation in the presence of a minor proportion, not in excess of about 10% based on said polymer, of a pentene.

6. In the alkylation of benzene with a polymer of a normal mono-olefin hydrocarbon, said polymer having at least 20 carbon atoms in the molecule in the presence of aluminum chloride and a minor proportion of hydrogen chloride, the improvement which comprises effecting said alkylation in the presence of a minor proportion not in excess of about 10%. based on said polymer. of an added propylene polymer having a molecular weight not in excess of about 130.

7. In the alkylation of a monocyclic aromatic hydrocarbon with a mono-olefin polymer having at least 20 carbon atoms in the molecule in the presence of aluminum chloride and a minor proportion of hydrogen chloride at a temperature in the range of about to about 150 F. under a pressure su'icient at least to maintain the liquid phase, the improvement which comprises eiIecting said alkylation in the presence of a minor proportion not in excess of about 10% based on said mono-olen polymer, of an added lower mono-oleiin hydrocarbon having a molecular weight not in excess oi.' about 130.

10 s. In the simenon of benzene with a. propri- 'enepolymerhavingatleastzocarbonatomsin the'molecule in the presence of aluminum chloride and a minor proportion of hydrogen chloride at a temperature in the range of about 0 to about F. under a pressure suiilcient at least to maintain the liquid phase, the improvement which comprises eiecting said alkylation in the presence of a minor proportion not in excess of about 10% based ony said propylene polymer. of an added lower Propylene polymer having a molecular weight not in excess of about 130.

9. In the alkylation of benzene with a Propyl- 'l ene polymer having at least 20 carbon atoms in the molecule in the presence of aluminum chloride and a minor proportion of hydrogen chloride at a temperature in the range of about 0 to about 100?. under a pressure suilicient at least to maintain the liquid phase, the improvement which comprises eiecting said alkylation in the presence of a minor Proportion not in excess of about 10%, based on said propylene polymer, .of a pentene.

10. In the alkylation of an aromatic hydrocarbon with a propylene polymer having atleast 20 carbon atoms in the molecule in the presence of a Friedel-Crafts catalyst, the improvement which comprises eilecting said alkylation in the the presence of a minor proportion, based on said propylene polymer, ot an added lower monoolen hydrocarbon having a molecular .weight not in excess of about 130. v

11. In the alkylation of a monocyclic aromatic hydrocarbon with a polymer of a normal mono-oleiln hydrocarbon. said polymer having at least about 20 carbon atoms in the molecule in the presence o1' a Friedel-Crafts catalyst, the improvement which comprises effecting `said alkylation in the presence of a minor proportion, not in excess of about 10 per cent based on .said polymer, or an added lower mono-olen hydrocarbon having a molecular weight not in excess of about 130.

12. The process of claim 11 wherein the Friedel-Crafts catalyst is aluminum chloride promoted by a minor proportion of hydrogen chloride.

PHILIPHIIL.

CES CITED 'I'he following references are of record in the ile oi this patent:

UNITE) STATES PATENTS Number Name Date 2,232,118 Kyrides Feb. 18, 1941 2,378,733 Sensei June 19, 1945 numbered patent requrmg correction as 'Certicate of Mmh o, 194s. l PHILIP HILL Y It is hereby certified that errors aper invvthce) specification of the above read whose; column" 2, line 33 for i.'e. read c. g.; column 8 line 45, Table 2 first column thereof, for (m1. 0.5 hr2/m1. so1n.)" read (mL 0.5 N n/ml. soln.) and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Office.

signed'md sealed this 27th day of April, ASD. 194s.

THOMAS F. MURPHY, Assistant Gommaoner of Patenti umn@2 line 5, for the word who 

